CN110845925B - Silver-containing nano composite antibacterial coating and preparation method thereof - Google Patents

Silver-containing nano composite antibacterial coating and preparation method thereof Download PDF

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CN110845925B
CN110845925B CN201810948400.3A CN201810948400A CN110845925B CN 110845925 B CN110845925 B CN 110845925B CN 201810948400 A CN201810948400 A CN 201810948400A CN 110845925 B CN110845925 B CN 110845925B
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methyl methacrylate
butyl acrylate
mass ratio
silver
emulsion
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CN110845925A (en
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郑俊萍
陈雨
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Tianjin University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention discloses a silver-containing nano composite antibacterial coating and a preparation method thereof, wherein polyacrylate and polymethyl methacrylate are used as a polyacrylate copolymerization matrix to synthesize maleic acid mono-fatty alcohol ester sodium salt methyl methacrylate, the methyl methacrylate is used as a polymerizable emulsifier and an auxiliary copolymerization monomer to regulate and control the dispersion of Ag nano particles in the polymer matrix through electrostatic interaction and steric hindrance interaction, and a nano composite emulsion is prepared through semi-continuous emulsion polymerization. Butyl acrylate and polymethyl methacrylate are used as main components of the coating, an emulsion polymerization method is adopted to prepare the nano composite coating, and Ag nano particles are dispersed in a polymer matrix to prepare the high-dispersion nano composite antibacterial coating.

Description

Silver-containing nano composite antibacterial coating and preparation method thereof
Technical Field
The invention relates to the technical field of nano composite materials, in particular to a silver-containing nano composite antibacterial coating and a preparation method thereof.
Background
With the continuous improvement of the living standard of human beings, people have higher requirements on living, working, living environmental quality and sanitary health. In the natural environment, various microbes such as bacteria and fungi are widely distributed, and not only are the microbes greatly damaged to various materials, but also various diseases caused by the action of the microbes cause great harm to human health. The coating is used as an important building material and has wide application in furniture production, material packaging and other aspects in daily life. Meanwhile, due to the consideration of safety and the requirement of environmental protection, the application of the antibacterial coating is more and more concerned.
The existing antibacterial coating is mainly an additive antibacterial coating, and an antibacterial agent which has an antibacterial function and can stably exist in a coating film is prepared by a certain processing technology mainly in an additive mode. In the additive antibacterial coating, the antibacterial agent is used as an auxiliary agent to be dispersed in a coating system, and the antibacterial agent comprises nano silver, antibiotics, quaternary ammonium salt and the like. The nano silver has extremely outstanding antibacterial performance, so the nano silver has very important irreplaceable effect in the field of antibacterial coatings. However, the structural difference between the nano silver and the matrix resin exists, and the nano silver is easy to agglomerate and has poor dispersibility due to small particle size, large specific surface area, large surface energy and strong surface effect of the nano particles. Therefore, how to uniformly disperse the nano silver in the matrix becomes a key problem for preparing the antibacterial coating. Most of the currently reported dispersion methods are nanoparticle surface modification, and most of the methods are complex in operation, complex in steps and large in environmental pollution, and bring much inconvenience to the preparation of the nano composite coating.
Disclosure of Invention
The invention overcomes the defects in the prior art, and provides a silver-containing nano composite antibacterial coating, a preparation method and application thereof, wherein Butyl Acrylate (BA) and polymethyl methacrylate (PMMA) are used as main components of the coating, an emulsion polymerization method is adopted to prepare the nano composite coating, and Ag nano particles are dispersed in a polymer matrix to prepare the high-dispersion nano composite antibacterial coating, because the nano silver and the matrix resin have structural difference, and the nano particles have small particle size, large specific surface area, large surface energy and strong surface action, so that the nano particles are easy to agglomerate and have poor dispersibility.
The purpose of the invention is realized by the following technical scheme.
The silver-containing nano composite antibacterial coating and the preparation method thereof are carried out according to the following steps:
step 1, taking butyl acrylate, methyl methacrylate and sodium lauryl maleate as comonomers, taking sodium lauryl maleate as an emulsifier, dissolving sodium lauryl maleate and an initiator in deionized water, adding butyl acrylate and methyl methacrylate, and stirring at a high speed to form a pre-emulsion;
wherein the oil phase consists of butyl acrylate, methyl methacrylate and sodium lauryl maleate, the water phase consists of water and an initiator, and the mass ratio of the water phase to the oil phase is (3-9): 1, the mass ratio of butyl acrylate to methyl methacrylate is (30-70): (30-70), the dosage of the sodium lauryl maleate is 2-10 wt% of the mass sum of the monomers of butyl acrylate and methyl methacrylate, and the dosage of the initiator is 0.1-1 wt% of the mass sum of the two monomers.
In step 1, the mass ratio of the water phase to the oil phase is (3-7): 1, the mass ratio of butyl acrylate to methyl methacrylate is equal to the mass ratio; the amount of the sodium lauryl maleate is 4-8 wt% of the sum of the mass of the butyl acrylate monomer and the methyl methacrylate monomer; the amount of the initiator is 0.2-0.5 wt% of the sum of the two monomers.
Step 2, taking lauryl maleate sodium salt as a dispersing agent, pre-dispersing silver nanoparticles in an aqueous solution to obtain a silver nanoparticle dispersion liquid, and adding butyl acrylate and methyl methacrylate into the dispersion liquid to form an emulsion polymerization system, wherein an oil phase consists of butyl acrylate, methyl methacrylate and lauryl maleate sodium salt, and a water phase consists of water and silver nanoparticles;
the mass ratio of the water phase to the oil phase is (3-9): 1, the mass ratio of butyl acrylate to methyl methacrylate is (30-70): (30-70), the dosage of the sodium lauryl maleate is 2-10 wt% of the mass sum of the butyl acrylate monomer and the methyl methacrylate monomer, and the silver nano particles are 1-20 wt% of the mass sum of the butyl acrylate monomer and the methyl methacrylate monomer.
In step 2, the mass ratio of the water phase to the oil phase is (3-7): 1, the mass ratio of butyl acrylate to methyl methacrylate is equal to the mass ratio; the amount of the sodium lauryl maleate is 4-8 wt% of the sum of the mass of the butyl acrylate monomer and the methyl methacrylate monomer; the silver nano particles account for 2-10 wt% of the sum of the mass of the butyl acrylate monomer and the methyl methacrylate monomer.
In step 1 and step 2, the mass ratio of butyl acrylate in step 1 and step 2 is (30-50): (50-70); the mass ratio of methyl methacrylate in step 1 and step 2 is (30-50): (50-70); the mass ratio of the sodium lauryl maleate in the step 1 and the step 2 is (30-50): (50-70).
In the step 1 and the step 2, the mass ratio of the butyl acrylate in the step 1 and the step 2 is equal to the mass ratio; the mass ratio of the methyl methacrylate in the step 1 and the step 2 is equal to the mass ratio; the mass ratio of the sodium lauryl maleate in the step 1 and the step 2 is equal to the mass ratio.
And 3, heating the emulsion polymerization system prepared in the step 2 to the initiation temperature of an initiator, adding the initiator to initiate polymerization, dripping the pre-emulsified liquid prepared in the step 1 into the emulsion polymerization system prepared in the step 2 in the polymerization reaction process, and stirring at a high speed for full reaction to obtain the polyacrylate nano composite emulsion.
The dosage of the initiator is 0.1 to 1 weight percent of the sum of the two monomers, the dripping time of the pre-emulsion is 0.5 to 1.5 hours, and the total emulsion polymerization time is 3 to 6 hours.
In step 3, the dripping time of the pre-emulsion is 0.5-1 h, and the total emulsion polymerization time is 3-4 h.
In step 3, the amount of initiator is 0.2 to 0.5% by weight of the sum of the two monomers.
The initiator used in the method is one of Azobisisobutyronitrile (AIBN), Azobisisoheptonitrile (ABVN), Benzoyl Peroxide (BPO), Ammonium Persulfate (APS) or potassium persulfate (KPS), preferably potassium persulfate (KPS), the polymerization temperature is 65-85 ℃, preferably 70-82 ℃, and the polyacrylate nano composite emulsion (P (MMA-co-BA-co-MAMS)/Ag) based on silver nanoparticles is obtained after full reaction.
And 4, carrying out centrifugal operation on the polyacrylate nano-composite emulsion obtained in the step 3, uniformly casting the composite emulsion on a substrate, and drying and forming to obtain the silver-containing nano-composite antibacterial coating (P (MMA-co-BA-co-MAMS)/Ag).
In step 4, the substrate is a glass plate or a teflon plate.
In step 4, the composite emulsion is evenly cast on a substrate and dried for 24 to 120 hours at the room temperature of 20 to 25 ℃, and then the substrate is placed at the temperature of 40 to 70 ℃ for vacuum drying for 24 to 120 hours to form the composite emulsion, preferably the composite emulsion is dried for 48 to 96 hours at the room temperature of 20 to 25 ℃ and then is placed at the temperature of 50 to 60 ℃ for vacuum drying for 48 to 96 hours.
The silver-containing nano composite antibacterial coating (P (MMA-co-BA-co-MAMS)/Ag) prepared by the invention is characterized.
FIG. 2 is a graph of the DLS test results of dynamic light scattering of Ag nanoparticles and silver-containing nanocomposite antibacterial coatings (P (MMA-co-BA-co-MAMS)/Ag). The DLS test result shows that the Ag nanoparticles are directly dispersed in water, the average particle size calculated according to the scattering intensity is 363.6nm, and the particle size is mainly concentrated at about 450nm, which indicates that the Ag nanoparticles have serious agglomeration and are very unevenly dispersed; the average particle size of the P (MMA-co-BA-co-MAMS)/Ag prepared by the method is 191-194nm, and the particle size is mainly concentrated at 268-272nm, so that the particle size reflects the total particle size of the polymer matrix microsphere and the Ag nano particles, and the size of the polymer microsphere is far larger than that of the Ag nano particles, so that the Ag nano particles can be judged to be well dispersed, the dispersion in the polymer matrix is uniform, and the agglomeration phenomenon is obviously improved.
FIG. 3 is an X-ray diffraction pattern of Ag nanoparticles and a silver-containing nanocomposite antibacterial coating (P (MMA-co-BA-co-MAMS)/Ag) prepared in the present invention. As can be seen from the XRD spectrum of the silver-containing nanocomposite antibacterial coating (P (MMA-co-BA-co-MAMS)/Ag), the broad peak around 2 θ ═ 20 ° should be the diffraction peak of the polymer matrix; the other four peaks completely correspond to the diffraction peaks of the Ag nanoparticles, and the weak peak at about 2 θ ═ 82 ° is not observed in the XRD spectrum because the intensity in the nanocomposite antibacterial coating is too low. From the results of XRD tests, it was clearly found that the silver-containing nanocomposite antibacterial coating was successfully prepared in the present invention and the product was pure without unwanted impurities.
FIG. 4 is a mechanical property test chart of the silver-containing nanocomposite antibacterial coating (P (MMA-co-BA-co-MAMS)/Ag) prepared in the present invention. The film sample is cut into dumbbell-shaped sample strips for mechanical property test, and the gauge length is 12mm and the width is 2 mm. The breaking strength of the sample can reach 6.0-9.0MPa, and the breaking elongation can reach more than 600%. According to the stress-strain curve, the tensile strength of the prepared P (MMA-co-BA-co-MAMS)/Ag is 7.60-7.80MPa, the elongation at break is 610-620%, the high mechanical strength is shown, and meanwhile, the toughness and the tensile property are excellent, which shows that the P (MMA-co-BA-co-MAMS)/Ag prepared by the invention has relatively outstanding mechanical properties.
And (3) performing an antibacterial zone experiment by adopting a film sample: (1) preparing a liquid culture medium and a solid culture medium, and sterilizing; (2) activating bacteria and enabling the bacteria to grow for 24 hours; (3) carrying out an inhibition zone experiment, which comprises the following specific steps: diluting the activated bacteria with a liquid culture medium for later use; adding the solid culture medium into a culture dish, and after the solid culture medium is solidified, adding 200 mu L of diluted bacterial liquid by using a pipette gun; uniformly coating the bacterial liquid on a solid culture medium by using a coater; then, flatly paving the sample film wafer on the surface of the flat plate; placing the culture dish in a shaking table at 37 ℃ for culturing for 18-24 h; and after the culture is finished, observing the situation of the inhibition zone around the sample. The antibacterial effect can be qualitatively reflected through the inhibition zone, the existence of the inhibition zone indicates that the antibacterial effect is better, and the larger the inhibition zone is, the better the antibacterial effect is. FIG. 5 is a graph showing the result of an antibacterial experiment using a silver-containing nanocomposite antibacterial coating (P (MMA-co-BA-co-MAMS)/Ag) prepared in the present invention, wherein (a) is a graph showing the result of an anti-E.coli experiment, and (b) is a graph showing the result of an anti-S.aureus experiment. Four parallel samples are selected for each kind of bacteria, the antibacterial effect of the prepared P (MMA-co-BA-co-MAMS)/Ag is verified through an inhibition zone experiment, and the graph can observe that the P (MMA-co-BA-co-MAMS)/Ag has better antibacterial effect on the two kinds of bacteria.
Compared with the prior art, the invention takes the copolymer of Methyl Methacrylate (MMA) and Butyl Acrylate (BA) as the base material of the coating, and takes the Methyl Methacrylate (MMA) as the hard monomer, thus keeping higher mechanical strength of the coating; butyl Acrylate (BA) is used as a soft monomer, so that the coating has better toughness and cohesiveness, and the novel silver-containing nano composite antibacterial coating material prepared in the invention has excellent performance; lauryl maleate sodium salt (MAMS) is used as a polymerizable emulsifier, so that the negative influence of emulsifier residue on the performance and environment of the coating is avoided; meanwhile, the sodium lauryl maleate (MAMS) is used as an auxiliary comonomer, and the dispersion of the Ag nanoparticles in the polymer matrix is regulated and controlled, so that the Ag nanoparticles are uniformly dispersed in the polymer matrix, the antibacterial function of Ag is fully exerted, and the antibacterial coating prepared by the method has a good antibacterial effect; the nano composite coating is prepared by combining room temperature casting and vacuum drying, and the method is simple and easy to operate; the method is simple, convenient, rapid, environment-friendly and practical, does not need complex procedures and expensive equipment, and has high efficiency and low cost.
Drawings
FIG. 1 is a drawing of the anionic monomer lauryl maleate sodium salt1H-NMR spectrum;
FIG. 2 is a graph showing the results of DLS test for dynamic light scattering of Ag nanoparticles and silver-containing nanocomposite antibacterial coating (P (MMA-co-BA-co-MAMS)/Ag), wherein (a) is a DLS test for Ag nanoparticles and (b) is a DLS test for P (MMA-co-BA-co-MAMS)/Ag;
FIG. 3 is an X-ray diffraction pattern of Ag nanoparticles (a) and a silver-containing nanocomposite antibacterial coating (P (MMA-co-BA-co-MAMS)/Ag) (b) prepared in the present invention;
FIG. 4 is a graph showing the mechanical properties of a silver-containing nanocomposite antibacterial coating (P (MMA-co-BA-co-MAMS)/Ag) prepared in the present invention;
FIG. 5 is a graph showing the result of an antibacterial experiment of a silver-containing nanocomposite antibacterial coating (P (MMA-co-BA-co-MAMS)/Ag) prepared in the present invention, wherein (a) is a graph showing the result of an anti-E.coli experiment and (b) is a graph showing the result of an anti-S.aureus experiment.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Preparation of lauryl maleate sodium salt (MAMS):
(1) 0.5mol of n-dodecanol and 0.5mol of maleic anhydride are added into a 500mL three-neck flask, stirred and heated to 50-60 ℃, and the temperature is raised to 80 ℃ after reactants are completely melted. After reacting for 1h, slowly adding 150mL of n-heptane, continuously stirring until a homogeneous transparent liquid is formed, stirring for 3h at room temperature (about 25 ℃), adding a proper amount of cold water or ice blocks to reduce the temperature to 15 ℃, continuously stirring for 2h, precipitating white crystals, and filtering to obtain a product, namely the maleic acid decaglycol ester.
(2) In a 100mL three-necked flask, 0.1mol of the prepared fatty acid monoester and 50mL of acetone were placed, stirred and heated to 60 ℃ to completely dissolve the fatty acid monoester. Preparing a NaOH solution with the mass fraction of 40%, adding 10g of the 40% NaOH solution into the reaction system, and accelerating stirring to disperse the precipitated solid. And after the dropwise addition of the NaOH solution, continuously stirring for 0.5h, cooling, performing suction filtration to obtain a white solid, and drying under vacuum to obtain a white powdery product, namely the lauryl maleate sodium salt MAMS.
To characterize the structure of the synthesized anionic monomer lauryl maleate sodium salt, about 15mg of the anionic monomer MAMS was weighed out and dissolved in deuterated water (D)2O) reagent, placing the reagent in a nuclear magnetic tube for sample preparation, wherein the liquid level of the solvent is not lower than 4cm, and facilitating nuclear magnetic hydrogen spectrum detection. The nuclear magnetic hydrogen spectrum of the anionic monomer MAMS is shown in FIG. 1.1H-NMR(D2O is 5.60(d, 1H), 6.41(d, 1H), 3.94(t, 2H), 1.47(m, 2H), 1.16(s, 2H), 0.74(t, 3H). From the 1H-NMR nuclear magnetic spectrum of MAMS, it can be seen that: the absorption peak at chemical shift delta 4.79 is D2An internal standard peak of O; the absorption peaks at chemical shifts δ 5.60 and δ 6.41 correspond to two hydrogens on the C ═ C double bond; the absorption peak at δ 3.94 corresponds to two hydrogens on the carbon atom directly attached to the oxygen atom; the two absorption peaks of delta 1.47 and delta 1.16 correspond to four hydrogens on the second and third methylene groups on the side of the long-chain alkyl group close to the oxygen atom; the absorption peak at δ 0.74 corresponds to three hydrogens on the methyl group at the end of the long chain alkyl group. Analysis shows that the peak area on the nuclear magnetic diagram is in direct proportion to the number of protons in the molecule, which proves that the target product, namely the lauryl maleate sodium salt is successfully synthesized and the product is pure.
Example 1
Preparing a P (MMA-co-BA-co-MAMS)/Ag nano composite antibacterial coating:
(1) weighing 0.5g of MAMS and 0.057g of initiator KPS, dissolving in 50mL of deionized water, weighing 5g of monomer butyl acrylate and 5g of methyl methacrylate, adding into a 100mL four-neck flask, stirring at 700rpm for pre-emulsification for 2h, and adding the pre-emulsion into a constant pressure dropping funnel for later use;
(2) then 0.5g of Ag nano particles and 0.5g of MAMS are dispersed in 50mL of deionized water, and are ultrasonically dispersed by a JY92-II N type ultrasonic cell crusher, and the set parameters are as follows: the power is 600W, the working time is 3s, the intermission time is 2s, ultrasonic treatment is carried out for 30min in an ice bath environment, and the ultrasonic dispersion liquid is added into a 250mL four-neck flask; weighing 5g of butyl acrylate and 5g of methyl methacrylate, adding the butyl acrylate and the methyl methacrylate into a 250mL four-neck flask, pre-emulsifying for 0.5h in a normal-temperature water bath, setting the stirring speed to 700rpm, and starting to heat after 0.5 h; weighing 0.057g of KPS when the temperature reaches 70 ℃, dissolving in a small amount of deionized water, adding into a four-neck flask, and starting to heat; when the temperature reaches 75 ℃, keeping the temperature and reacting for 0.5h, beginning to dropwise add the pre-emulsion to be used into the four-neck flask, and continuing to react for 1 h; after 1h, after the pre-emulsion is added dropwise, heating; the temperature reaches 82 ℃, and the reaction is carried out for 2 hours under the condition of heat preservation; after 2h, stopping heating, and stirring until the temperature is cooled to room temperature;
(3) discharging, filtering with a 300-mesh nylon filter screen, and adjusting the pH value to 7-8 with ammonia water to obtain the nano composite emulsion, which is recorded as P (MMA-co-BA-co-MAMS)/Ag.
(4) Casting the prepared silver-containing nano composite emulsion on a glass plate and a polytetrafluoroethylene plate at room temperature, and drying for 72 h; and then transferring the casting coating into a vacuum drying oven, thoroughly removing water and unreacted monomer micromolecules, setting the drying temperature at 50 ℃, and drying for 72 hours to obtain the P (MMA-co-BA-co-MAMS)/Ag nano composite antibacterial coating.
Example 2
(1) Weighing 0.5g of MAMS and 0.057g of initiator KPS, dissolving in 50mL of deionized water, weighing 5g of monomer butyl acrylate and 5g of methyl methacrylate, adding into a 100mL four-neck flask, stirring at 700rpm for pre-emulsification for 2h, and adding the pre-emulsion into a constant pressure dropping funnel for later use;
(2) then 0.25g of Ag nano particles and 0.5g of MAMS are dispersed in 50mL of deionized water, and are ultrasonically dispersed by using a JY92-II N type ultrasonic cell crusher, and the set parameters are as follows: the power is 600W, the working time is 3s, the intermission time is 2s, ultrasonic treatment is carried out for 30min in an ice bath environment, and the ultrasonic dispersion liquid is added into a 250mL four-neck flask; weighing 5g of butyl acrylate and 5g of methyl methacrylate, adding the butyl acrylate and the methyl methacrylate into a 250mL four-neck flask, pre-emulsifying for 0.5h in a normal-temperature water bath, setting the stirring speed to 700rpm, and starting to heat after 0.5 h; weighing 0.057g of KPS when the temperature reaches 65 ℃, dissolving in a small amount of deionized water, adding into a four-neck flask, and starting to heat; when the temperature reaches 70 ℃, keeping the temperature and reacting for 0.5h, beginning to dropwise add the pre-emulsion to be used into the four-neck flask, and continuing to react for 1 h; after 1h, after the pre-emulsion is added dropwise, heating; the temperature reaches 85 ℃, and the reaction is carried out for 2 hours under the condition of heat preservation; after 2h, stopping heating, and stirring until the temperature is cooled to room temperature;
(3) discharging, filtering with a 300-mesh nylon filter screen, and adjusting the pH value to 7-8 with ammonia water to obtain the nano composite emulsion, which is recorded as P (MMA-co-BA-co-MAMS)/Ag.
(4) Casting the prepared silver-containing nano composite emulsion on a glass plate and a polytetrafluoroethylene plate at room temperature, and drying for 72 h; and then transferring the casting coating into a vacuum drying oven, thoroughly removing water and unreacted monomer micromolecules, setting the drying temperature at 50 ℃, and drying for 72 hours to obtain the P (MMA-co-BA-co-MAMS)/Ag nano composite antibacterial coating.
Example 3
(1) Weighing 0.5g of MAMS and 0.057g of initiator KPS, dissolving in 50mL of deionized water, weighing 5g of monomer butyl acrylate and 5g of methyl methacrylate, adding into a 100mL four-neck flask, stirring at 700rpm for pre-emulsification for 2h, and adding the pre-emulsion into a constant pressure dropping funnel for later use;
(2) then 1.0g of Ag nano particles and 0.5g of MAMS are dispersed in 50mL of deionized water, and are ultrasonically dispersed by using a JY92-II N type ultrasonic cell crusher, and the set parameters are as follows: the power is 600W, the working time is 3s, the intermission time is 2s, ultrasonic treatment is carried out for 30min in an ice bath environment, and the ultrasonic dispersion liquid is added into a 250mL four-neck flask; weighing 5g of butyl acrylate and 5g of methyl methacrylate, adding the butyl acrylate and the methyl methacrylate into a 250mL four-neck flask, pre-emulsifying for 0.5h in a normal-temperature water bath, setting the stirring speed to 700rpm, and starting to heat after 0.5 h; weighing 0.057g of KPS when the temperature reaches 66 ℃, dissolving in a small amount of deionized water, adding into a four-neck flask, and starting to heat; when the temperature reaches 71 ℃, keeping the temperature and reacting for 0.5h, then dropwise adding the pre-emulsion to be used into a four-neck flask, and continuing to react for 1 h; after 1h, after the pre-emulsion is added dropwise, heating; the temperature reaches 81 ℃, and the reaction is carried out for 2 hours under the condition of heat preservation; after 2h, stopping heating, and stirring until the temperature is cooled to room temperature;
(3) discharging, filtering with a 300-mesh nylon filter screen, and adjusting the pH value to 7-8 with ammonia water to obtain the nano composite emulsion, which is recorded as P (MMA-co-BA-co-MAMS)/Ag.
(4) Casting the prepared silver-containing nano composite emulsion on a glass plate and a polytetrafluoroethylene plate at room temperature, and drying for 72 h; and then transferring the casting coating into a vacuum drying oven, thoroughly removing water and unreacted monomer micromolecules, setting the drying temperature at 50 ℃, and drying for 72 hours to obtain the P (MMA-co-BA-co-MAMS)/Ag nano composite antibacterial coating.
Example 4
(1) Weighing 0.5g of MAMS and 0.057g of initiator KPS, dissolving in 50mL of deionized water, weighing 5g of monomer butyl acrylate and 5g of methyl methacrylate, adding into a 100mL four-neck flask, stirring at 700rpm for pre-emulsification for 2h, and adding the pre-emulsion into a constant pressure dropping funnel for later use;
(2) then 1.5g of Ag nano particles and 0.5g of MAMS are dispersed in 50mL of deionized water, and are ultrasonically dispersed by using a JY92-II N type ultrasonic cell crusher, and the set parameters are as follows: the power is 600W, the working time is 3s, the intermission time is 2s, ultrasonic treatment is carried out for 30min in an ice bath environment, and the ultrasonic dispersion liquid is added into a 250mL four-neck flask; weighing 5g of butyl acrylate and 5g of methyl methacrylate, adding the butyl acrylate and the methyl methacrylate into a 250mL four-neck flask, pre-emulsifying for 0.5h in a normal-temperature water bath, setting the stirring speed to 700rpm, and starting to heat after 0.5 h; weighing 0.057g of KPS when the temperature reaches 67 ℃, dissolving in a small amount of deionized water, adding into a four-neck flask, and starting to heat; when the temperature reaches 72 ℃, keeping the temperature and reacting for 0.5h, beginning to dropwise add the pre-emulsion to be used into the four-neck flask, and continuing to react for 1 h; after 1h, after the pre-emulsion is added dropwise, heating; the temperature reaches 82 ℃, and the reaction is carried out for 2 hours under the condition of heat preservation; after 2h, stopping heating, and stirring until the temperature is cooled to room temperature;
(3) discharging, filtering with a 300-mesh nylon filter screen, and adjusting the pH value to 7-8 with ammonia water to obtain the nano composite emulsion, which is recorded as P (MMA-co-BA-co-MAMS)/Ag.
(4) Casting the prepared silver-containing nano composite emulsion on a glass plate and a polytetrafluoroethylene plate at room temperature, and drying for 72 h; and then transferring the casting coating into a vacuum drying oven, thoroughly removing water and unreacted monomer micromolecules, setting the drying temperature at 50 ℃, and drying for 72 hours to obtain the P (MMA-co-BA-co-MAMS)/Ag nano composite antibacterial coating.
Example 5
(1) Weighing 0.5g of MAMS and 0.057g of initiator KPS, dissolving in 50mL of deionized water, weighing 6g of monomer butyl acrylate and 4g of methyl methacrylate, adding into a 100mL four-neck flask, stirring at 700rpm for pre-emulsification for 2h, and adding the pre-emulsion into a constant pressure dropping funnel for later use;
(2) then 0.5g of Ag nano particles and 0.5g of MAMS are dispersed in 50mL of deionized water, and are ultrasonically dispersed by a JY92-II N type ultrasonic cell crusher, and the set parameters are as follows: the power is 600W, the working time is 3s, the intermission time is 2s, ultrasonic treatment is carried out for 30min in an ice bath environment, and the ultrasonic dispersion liquid is added into a 250mL four-neck flask; weighing 6g of butyl acrylate and 4g of methyl methacrylate, adding the butyl acrylate and the methyl methacrylate into a 250mL four-neck flask, pre-emulsifying for 0.5h in a normal-temperature water bath, setting the stirring speed to 700rpm, and starting to heat after 0.5 h; weighing 0.057g of KPS when the temperature reaches 69 ℃, dissolving in a small amount of deionized water, adding into a four-neck flask, and starting to heat; when the temperature reaches 74 ℃, keeping the temperature and reacting for 0.5h, beginning to dropwise add the pre-emulsion to be used into the four-neck flask, and continuing to react for 1 h; after 1h, after the pre-emulsion is added dropwise, heating; the temperature reaches 84 ℃, and the reaction is carried out for 2 hours under the condition of heat preservation; after 2h, stopping heating, and stirring until the temperature is cooled to room temperature;
(3) discharging, filtering with a 300-mesh nylon filter screen, and adjusting the pH value to 7-8 with ammonia water to obtain the nano composite emulsion, which is recorded as P (MMA-co-BA-co-MAMS)/Ag.
(4) Casting the prepared silver-containing nano composite emulsion on a glass plate and a polytetrafluoroethylene plate at room temperature, and drying for 72 h; and then transferring the casting coating into a vacuum drying oven, thoroughly removing water and unreacted monomer micromolecules, setting the drying temperature at 50 ℃, and drying for 72 hours to obtain the P (MMA-co-BA-co-MAMS)/Ag nano composite antibacterial coating.
Example 6
(1) Weighing 0.5g of MAMS and 0.057g of initiator KPS, dissolving in 50mL of deionized water, weighing 7g of monomer butyl acrylate and 3g of methyl methacrylate, adding into a 100mL four-neck flask, stirring at 700rpm for pre-emulsification for 2h, and adding the pre-emulsion into a constant pressure dropping funnel for later use;
(2) then 0.5g of Ag nano particles and 0.5g of MAMS are dispersed in 50mL of deionized water, and are ultrasonically dispersed by a JY92-II N type ultrasonic cell crusher, and the set parameters are as follows: the power is 600W, the working time is 3s, the intermission time is 2s, ultrasonic treatment is carried out for 30min in an ice bath environment, and the ultrasonic dispersion liquid is added into a 250mL four-neck flask; weighing 7g of butyl acrylate and 3g of methyl methacrylate, adding the butyl acrylate and the methyl methacrylate into a 250mL four-neck flask, pre-emulsifying for 0.5h in a normal-temperature water bath, setting the stirring speed to 700rpm, and starting to heat after 0.5 h; weighing 0.057g of KPS when the temperature reaches 69 ℃, dissolving in a small amount of deionized water, adding into a four-neck flask, and starting to heat; when the temperature reaches 73 ℃, keeping the temperature and reacting for 0.5h, beginning to dropwise add the pre-emulsion to be used into the four-neck flask, and continuing to react for 1 h; after 1h, after the pre-emulsion is added dropwise, heating; the temperature reaches 84 ℃, and the reaction is carried out for 2 hours under the condition of heat preservation; after 2h, stopping heating, and stirring until the temperature is cooled to room temperature;
(3) discharging, filtering with a 300-mesh nylon filter screen, and adjusting the pH value to 7-8 with ammonia water to obtain the nano composite emulsion, which is recorded as P (MMA-co-BA-co-MAMS)/Ag.
(4) Casting the prepared silver-containing nano composite emulsion on a glass plate and a polytetrafluoroethylene plate at room temperature, and drying for 72 h; and then transferring the casting coating into a vacuum drying oven, thoroughly removing water and unreacted monomer micromolecules, setting the drying temperature at 50 ℃, and drying for 72 hours to obtain the P (MMA-co-BA-co-MAMS)/Ag nano composite antibacterial coating.
Example 7
(1) Weighing 0.5g of MAMS and 0.057g of initiator KPS, dissolving in 50mL of deionized water, weighing 4g of monomer butyl acrylate and 6g of methyl methacrylate, adding into a 100mL four-neck flask, stirring at 700rpm for pre-emulsification for 2h, and adding the pre-emulsion into a constant pressure dropping funnel for later use;
(2) then 0.5g of Ag nano particles and 0.5g of MAMS are dispersed in 50mL of deionized water, and are ultrasonically dispersed by a JY92-II N type ultrasonic cell crusher, and the set parameters are as follows: the power is 600W, the working time is 3s, the intermission time is 2s, ultrasonic treatment is carried out for 30min in an ice bath environment, and the ultrasonic dispersion liquid is added into a 250mL four-neck flask; weighing 4g of butyl acrylate and 6g of methyl methacrylate, adding the butyl acrylate and the methyl methacrylate into a 250mL four-neck flask, pre-emulsifying for 0.5h in a normal-temperature water bath, setting the stirring speed to 700rpm, and starting to heat after 0.5 h; weighing 0.057g of KPS when the temperature reaches 70 ℃, dissolving in a small amount of deionized water, adding into a four-neck flask, and starting to heat; when the temperature reaches 76 ℃, keeping the temperature and reacting for 0.5h, beginning to dropwise add the pre-emulsion to be used into the four-neck flask, and continuing to react for 1 h; after 1h, after the pre-emulsion is added dropwise, heating; the temperature reaches 85 ℃, and the reaction is carried out for 2 hours under the condition of heat preservation; after 2h, stopping heating, and stirring until the temperature is cooled to room temperature;
(3) discharging, filtering with a 300-mesh nylon filter screen, and adjusting the pH value to 7-8 with ammonia water to obtain the nano composite emulsion, which is recorded as P (MMA-co-BA-co-MAMS)/Ag.
(4) Casting the prepared silver-containing nano composite emulsion on a glass plate and a polytetrafluoroethylene plate at room temperature, and drying for 72 h; and then transferring the casting coating into a vacuum drying oven, thoroughly removing water and unreacted monomer micromolecules, setting the drying temperature at 50 ℃, and drying for 72 hours to obtain the P (MMA-co-BA-co-MAMS)/Ag nano composite antibacterial coating.
Example 8
(1) Weighing 0.5g of MAMS and 0.057g of initiator KPS, dissolving in 50mL of deionized water, weighing 3g of monomer butyl acrylate and 7g of methyl methacrylate, adding into a 100mL four-neck flask, stirring at 700rpm for pre-emulsification for 2h, and adding the pre-emulsion into a constant pressure dropping funnel for later use;
(2) then 0.5g of Ag nano particles and 0.5g of MAMS are dispersed in 50mL of deionized water, and are ultrasonically dispersed by a JY92-II N type ultrasonic cell crusher, and the set parameters are as follows: the power is 600W, the working time is 3s, the intermission time is 2s, ultrasonic treatment is carried out for 30min in an ice bath environment, and the ultrasonic dispersion liquid is added into a 250mL four-neck flask; weighing 3g of butyl acrylate and 7g of methyl methacrylate, adding the butyl acrylate and the methyl methacrylate into a 250mL four-neck flask, pre-emulsifying for 0.5h in a normal-temperature water bath, setting the stirring speed to 700rpm, and starting to heat after 0.5 h; weighing 0.057g of KPS when the temperature reaches 70 ℃, dissolving in a small amount of deionized water, adding into a four-neck flask, and starting to heat; when the temperature reaches 75 ℃, keeping the temperature and reacting for 0.5h, beginning to dropwise add the pre-emulsion to be used into the four-neck flask, and continuing to react for 1 h; after 1h, after the pre-emulsion is added dropwise, heating; the temperature reaches 82 ℃, and the reaction is carried out for 2 hours under the condition of heat preservation; after 2h, stopping heating, and stirring until the temperature is cooled to room temperature;
(3) discharging, filtering with a 300-mesh nylon filter screen, and adjusting the pH value to 7-8 with ammonia water to obtain the nano composite emulsion, which is recorded as P (MMA-co-BA-co-MAMS)/Ag.
(4) Casting the prepared silver-containing nano composite emulsion on a glass plate and a polytetrafluoroethylene plate at room temperature, and drying for 72 h; and then transferring the casting coating into a vacuum drying oven, thoroughly removing water and unreacted monomer micromolecules, setting the drying temperature at 50 ℃, and drying for 72 hours to obtain the P (MMA-co-BA-co-MAMS)/Ag nano composite antibacterial coating.
Example 9
(1) Weighing 0.5g of MAMS and 0.057g of initiator BPO, dissolving in 50mL of deionized water, weighing 5g of monomer butyl acrylate and 5g of methyl methacrylate, adding into a 100mL four-neck flask, stirring at 700rpm for pre-emulsification for 2h, and adding the pre-emulsion into a constant-pressure dropping funnel for later use;
(2) then 0.5g of Ag nano particles and 0.5g of MAMS are dispersed in 50mL of deionized water, and are ultrasonically dispersed by a JY92-II N type ultrasonic cell crusher, and the set parameters are as follows: the power is 600W, the working time is 3s, the intermission time is 2s, ultrasonic treatment is carried out for 30min in an ice bath environment, and the ultrasonic dispersion liquid is added into a 250mL four-neck flask; weighing 5g of butyl acrylate and 5g of methyl methacrylate, adding the butyl acrylate and the methyl methacrylate into a 250mL four-neck flask, pre-emulsifying for 0.5h in a normal-temperature water bath, setting the stirring speed to 700rpm, and starting to heat after 0.5 h; weighing 0.057g of BPO at the temperature of 68 ℃, dissolving in a small amount of deionized water, adding into a four-neck flask, and starting to heat; when the temperature reaches 72 ℃, keeping the temperature and reacting for 0.5h, beginning to dropwise add the pre-emulsion to be used into the four-neck flask, and continuing to react for 1 h; after 1h, after the pre-emulsion is added dropwise, heating; the temperature reaches 82 ℃, and the reaction is carried out for 2 hours under the condition of heat preservation; after 2h, stopping heating, and stirring until the temperature is cooled to room temperature;
(3) discharging, filtering with a 300-mesh nylon filter screen, and adjusting the pH value to 7-8 with ammonia water to obtain the nano composite emulsion, which is recorded as P (MMA-co-BA-co-MAMS)/Ag.
(4) Casting the prepared silver-containing nano composite emulsion on a glass plate and a polytetrafluoroethylene plate at room temperature, and drying for 72 h; and then transferring the casting coating into a vacuum drying oven, thoroughly removing water and unreacted monomer micromolecules, setting the drying temperature at 50 ℃, and drying for 72 hours to obtain the P (MMA-co-BA-co-MAMS)/Ag nano composite antibacterial coating.
Example 10
(1) Weighing 1.0g of MAMS and 0.057g of initiator KPS, dissolving in 50mL of deionized water, weighing 5g of monomer butyl acrylate and 5g of methyl methacrylate, adding into a 100mL four-neck flask, stirring at 700rpm for pre-emulsification for 2h, and adding the pre-emulsion into a constant pressure dropping funnel for later use;
(2) then 0.5g of Ag nano particles and 1.0g of MAMS are dispersed in 50mL of deionized water, and are ultrasonically dispersed by using a JY92-II N type ultrasonic cell crusher, and the set parameters are as follows: the power is 600W, the working time is 3s, the intermission time is 2s, ultrasonic treatment is carried out for 30min in an ice bath environment, and the ultrasonic dispersion liquid is added into a 250mL four-neck flask; weighing 5g of butyl acrylate and 5g of methyl methacrylate, adding the butyl acrylate and the methyl methacrylate into a 250mL four-neck flask, pre-emulsifying for 0.5h in a normal-temperature water bath, setting the stirring speed to 700rpm, and starting to heat after 0.5 h; weighing 0.057g of KPS when the temperature reaches 67 ℃, dissolving in a small amount of deionized water, adding into a four-neck flask, and starting to heat; when the temperature reaches 71 ℃, keeping the temperature and reacting for 0.5h, then dropwise adding the pre-emulsion to be used into a four-neck flask, and continuing to react for 1 h; after 1h, after the pre-emulsion is added dropwise, heating; the temperature reaches 80 ℃, and the reaction is carried out for 2 hours under the condition of heat preservation; after 2h, stopping heating, and stirring until the temperature is cooled to room temperature;
(3) discharging, filtering with a 300-mesh nylon filter screen, and adjusting the pH value to 7-8 with ammonia water to obtain the nano composite emulsion, which is recorded as P (MMA-co-BA-co-MAMS)/Ag.
(4) Casting the prepared silver-containing nano composite emulsion on a glass plate and a polytetrafluoroethylene plate at room temperature, and drying for 72 h; and then transferring the casting coating into a vacuum drying oven, thoroughly removing water and unreacted monomer micromolecules, setting the drying temperature at 50 ℃, and drying for 72 hours to obtain the P (MMA-co-BA-co-MAMS)/Ag nano composite antibacterial coating.
Example 11
(1) Weighing 0.4g of MAMS and 0.057g of initiator KPS, dissolving in 50mL of deionized water, weighing 5g of monomer butyl acrylate and 5g of methyl methacrylate, adding into a 100mL four-neck flask, stirring at 700rpm for pre-emulsification for 2h, and adding the pre-emulsion into a constant pressure dropping funnel for later use;
(2) then 0.4g of Ag nano particles and 0.5g of MAMS are dispersed in 50mL of deionized water, and are ultrasonically dispersed by using a JY92-II N type ultrasonic cell crusher, and the set parameters are as follows: the power is 600W, the working time is 3s, the intermission time is 2s, ultrasonic treatment is carried out for 30min in an ice bath environment, and the ultrasonic dispersion liquid is added into a 250mL four-neck flask; weighing 5g of butyl acrylate and 5g of methyl methacrylate, adding the butyl acrylate and the methyl methacrylate into a 250mL four-neck flask, pre-emulsifying for 0.5h in a normal-temperature water bath, setting the stirring speed to 700rpm, and starting to heat after 0.5 h; weighing 0.057g of KPS when the temperature reaches 71 ℃, dissolving in a small amount of deionized water, adding into a four-neck flask, and starting to heat; when the temperature reaches 77 ℃, keeping the temperature and reacting for 0.5h, beginning to dropwise add the pre-emulsion to be used into the four-neck flask, and continuing to react for 1 h; after 1h, after the pre-emulsion is added dropwise, heating; the temperature reaches 82 ℃, and the reaction is carried out for 2 hours under the condition of heat preservation; after 2h, stopping heating, and stirring until the temperature is cooled to room temperature;
(3) discharging, filtering with a 300-mesh nylon filter screen, and adjusting the pH value to 7-8 with ammonia water to obtain the nano composite emulsion, which is recorded as P (MMA-co-BA-co-MAMS)/Ag.
(4) Casting the prepared silver-containing nano composite emulsion on a glass plate and a polytetrafluoroethylene plate at room temperature, and drying for 72 h; and then transferring the casting coating into a vacuum drying oven, thoroughly removing water and unreacted monomer micromolecules, setting the drying temperature at 50 ℃, and drying for 72 hours to obtain the P (MMA-co-BA-co-MAMS)/Ag nano composite antibacterial coating.
Example 12
(1) Weighing 0.5g of MAMS and 0.057g of initiator KPS, dissolving in 50mL of deionized water, weighing 5g of monomer butyl acrylate and 5g of methyl methacrylate, adding into a 100mL four-neck flask, stirring at 700rpm for pre-emulsification for 2h, and adding the pre-emulsion into a constant pressure dropping funnel for later use;
(2) then 0.5g of Ag nano particles and 0.5g of MAMS are dispersed in 50mL of deionized water, and are ultrasonically dispersed by a JY92-II N type ultrasonic cell crusher, and the set parameters are as follows: the power is 600W, the working time is 3s, the intermission time is 2s, ultrasonic treatment is carried out for 30min in an ice bath environment, and the ultrasonic dispersion liquid is added into a 250mL four-neck flask; weighing 5g of butyl acrylate and 5g of methyl methacrylate, adding the butyl acrylate and the methyl methacrylate into a 250mL four-neck flask, pre-emulsifying for 0.5h in a normal-temperature water bath, setting the stirring speed to 700rpm, and starting to heat after 0.5 h; weighing 0.057g of KPS when the temperature reaches 70 ℃, dissolving in a small amount of deionized water, adding into a four-neck flask, and starting to heat; when the temperature reaches 75 ℃, keeping the temperature and reacting for 0.5h, beginning to dropwise add the pre-emulsion to be used into the four-neck flask, and continuing to react for 1 h; after 1h, after the pre-emulsion is added dropwise, heating; the temperature reaches 82 ℃, and the reaction is carried out for 2 hours under the condition of heat preservation; after 2h, stopping heating, and stirring until the temperature is cooled to room temperature;
(3) discharging, filtering with a 300-mesh nylon filter screen, and adjusting the pH value to 7-8 with ammonia water to obtain the nano composite emulsion, which is recorded as P (MMA-co-BA-co-MAMS)/Ag.
(4) Casting the prepared silver-containing nano composite emulsion on a glass plate and a polytetrafluoroethylene plate at room temperature, and drying for 72 h; and then transferring the casting coating into a vacuum drying oven, thoroughly removing water and unreacted monomer micromolecules, setting the drying temperature at 60 ℃, and drying for 72 hours to obtain the P (MMA-co-BA-co-MAMS)/Ag nano composite antibacterial coating.
The preparation of the antibacterial coating can be realized by adjusting the process parameters according to the content of the invention, and the antibacterial coating shows the performance basically consistent with the invention. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.

Claims (16)

1. The silver-containing nano composite antibacterial coating is characterized by comprising the following steps:
step 1, taking butyl acrylate, methyl methacrylate and sodium lauryl maleate as comonomers, taking sodium lauryl maleate as an emulsifier, dissolving sodium lauryl maleate and an initiator in deionized water, adding butyl acrylate and methyl methacrylate, and stirring at a high speed to form a pre-emulsion; wherein the oil phase consists of butyl acrylate, methyl methacrylate and sodium lauryl maleate, the water phase consists of water and an initiator, and the mass ratio of the water phase to the oil phase is (3-9): 1, the mass ratio of butyl acrylate to methyl methacrylate is (30-70): (30-70), the amount of the sodium lauryl maleate is 2-10 wt% of the sum of the mass of the butyl acrylate monomer and the methyl methacrylate monomer, and the amount of the initiator is 0.1-1 wt% of the sum of the mass of the two monomers;
step 2, taking lauryl maleate sodium salt as a dispersing agent, pre-dispersing silver nanoparticles in an aqueous solution to obtain a silver nanoparticle dispersion liquid, and adding butyl acrylate and methyl methacrylate into the dispersion liquid to form an emulsion polymerization system, wherein an oil phase consists of butyl acrylate, methyl methacrylate and lauryl maleate sodium salt, and a water phase consists of water and silver nanoparticles; the mass ratio of the water phase to the oil phase is (3-9): 1, the mass ratio of butyl acrylate to methyl methacrylate is (30-70): (30-70), the using amount of the sodium lauryl maleate is 2-10 wt% of the mass sum of the butyl acrylate monomer and the methyl methacrylate monomer, and the silver nano particles are 1-20 wt% of the mass sum of the butyl acrylate monomer and the methyl methacrylate monomer; in step 1 and step 2, the mass ratio of butyl acrylate in step 1 and step 2 is (30-50): (50-70); the mass ratio of methyl methacrylate in step 1 and step 2 is (30-50): (50-70); the mass ratio of the sodium lauryl maleate in the step 1 and the step 2 is (30-50): (50-70);
step 3, heating the emulsion polymerization system prepared in the step 2 to the initiation temperature of an initiator, adding the initiator to initiate polymerization, dripping the pre-emulsified liquid prepared in the step 1 into the emulsion polymerization system prepared in the step 2 in the polymerization reaction process, and stirring at a high speed for full reaction to obtain the polyacrylate nano composite emulsion; the dosage of the initiator is 0.1 to 1 weight percent of the mass sum of the two monomers, the dripping time of the pre-emulsion is 0.5 to 1.5 hours, and the total emulsion polymerization time is 3 to 6 hours;
and 4, carrying out centrifugal operation on the polyacrylate nano-composite emulsion obtained in the step 3, uniformly casting the composite emulsion on a substrate, and drying and forming to obtain the silver-containing nano-composite antibacterial coating P (MMA-co-BA-co-MAMS)/Ag.
2. The silver-containing nanocomposite antibacterial coating according to claim 1, wherein in step 1, the mass ratio of the aqueous phase to the oil phase is (3-7): 1, the mass ratio of butyl acrylate to methyl methacrylate is equal to the mass ratio; the amount of the sodium lauryl maleate is 4-8 wt% of the sum of the mass of the butyl acrylate monomer and the methyl methacrylate monomer; the amount of the initiator is 0.2-0.5 wt% of the sum of the two monomers; in step 2, the mass ratio of the water phase to the oil phase is (3-7): 1, the mass ratio of butyl acrylate to methyl methacrylate is equal to the mass ratio; the amount of the sodium lauryl maleate is 4-8 wt% of the sum of the mass of the butyl acrylate monomer and the methyl methacrylate monomer; the silver nano particles account for 2-10 wt% of the sum of the mass of the butyl acrylate monomer and the methyl methacrylate monomer.
3. The silver-containing nanocomposite antimicrobial coating according to claim 1, wherein in step 1 and step 2, the mass ratio of butyl acrylate in step 1 and step 2 is equal to the mass ratio; the mass ratio of the methyl methacrylate in the step 1 and the step 2 is equal to the mass ratio; the mass ratio of the sodium lauryl maleate in the step 1 and the step 2 is equal to the mass ratio.
4. The silver-containing nanocomposite antibacterial coating according to claim 1, wherein in step 3, the dropping time of the pre-emulsion is 0.5 to 1 hour, the total emulsion polymerization time is 3 to 4 hours, the amount of the initiator is 0.2 to 0.5 wt% of the sum of the two monomers, and the initiator is one of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, ammonium persulfate or potassium persulfate.
5. The silver-containing nanocomposite antimicrobial coating according to claim 4, wherein in step 3, the initiator is potassium persulfate and the polymerization temperature is 65-85 ℃.
6. The silver-containing nanocomposite antimicrobial coating according to claim 5, wherein in step 3, the polymerization temperature is 70 to 82 ℃.
7. The silver-containing nanocomposite antibacterial coating of claim 1, wherein in step 4, the substrate is a glass plate or a polytetrafluoroethylene plate, the composite emulsion is uniformly cast on the substrate, dried at room temperature of 20-25 ℃ for 24-120 h, and then dried under vacuum at 40-70 ℃ for 24-120 h to form the silver-containing nanocomposite antibacterial coating.
8. The silver-containing nanocomposite antibacterial coating according to claim 7, wherein in step 4, the composite emulsion is uniformly cast on a substrate, dried at room temperature of 20-25 ℃ for 48-96 h, and then vacuum-dried at 50-60 ℃ for 48-96 h to form the silver-containing nanocomposite antibacterial coating.
9. The preparation method of the silver-containing nano composite antibacterial coating is characterized by comprising the following steps:
step 1, taking butyl acrylate, methyl methacrylate and sodium lauryl maleate as comonomers, taking sodium lauryl maleate as an emulsifier, dissolving sodium lauryl maleate and an initiator in deionized water, adding butyl acrylate and methyl methacrylate, and stirring at a high speed to form a pre-emulsion; wherein the oil phase consists of butyl acrylate, methyl methacrylate and sodium lauryl maleate, the water phase consists of water and an initiator, and the mass ratio of the water phase to the oil phase is (3-9): 1, the mass ratio of butyl acrylate to methyl methacrylate is (30-70): (30-70), the amount of the sodium lauryl maleate is 2-10 wt% of the sum of the mass of the butyl acrylate monomer and the methyl methacrylate monomer, and the amount of the initiator is 0.1-1 wt% of the sum of the mass of the two monomers;
step 2, taking lauryl maleate sodium salt as a dispersing agent, pre-dispersing silver nanoparticles in an aqueous solution to obtain a silver nanoparticle dispersion liquid, and adding butyl acrylate and methyl methacrylate into the dispersion liquid to form an emulsion polymerization system, wherein an oil phase consists of butyl acrylate, methyl methacrylate and lauryl maleate sodium salt, and a water phase consists of water and silver nanoparticles; the mass ratio of the water phase to the oil phase is (3-9): 1, the mass ratio of butyl acrylate to methyl methacrylate is (30-70): (30-70), the using amount of the sodium lauryl maleate is 2-10 wt% of the mass sum of the butyl acrylate monomer and the methyl methacrylate monomer, and the silver nano particles are 1-20 wt% of the mass sum of the butyl acrylate monomer and the methyl methacrylate monomer; in step 1 and step 2, the mass ratio of butyl acrylate in step 1 and step 2 is (30-50): (50-70); the mass ratio of methyl methacrylate in step 1 and step 2 is (30-50): (50-70); the mass ratio of the sodium lauryl maleate in the step 1 and the step 2 is (30-50): (50-70);
step 3, heating the emulsion polymerization system prepared in the step 2 to the initiation temperature of an initiator, adding the initiator to initiate polymerization, dripping the pre-emulsified liquid prepared in the step 1 into the emulsion polymerization system prepared in the step 2 in the polymerization reaction process, and stirring at a high speed for full reaction to obtain the polyacrylate nano composite emulsion; the dosage of the initiator is 0.1 to 1 weight percent of the mass sum of the two monomers, the dripping time of the pre-emulsion is 0.5 to 1.5 hours, and the total emulsion polymerization time is 3 to 6 hours;
and 4, carrying out centrifugal operation on the polyacrylate nano-composite emulsion obtained in the step 3, uniformly casting the composite emulsion on a substrate, and drying and forming to obtain the silver-containing nano-composite antibacterial coating P (MMA-co-BA-co-MAMS)/Ag.
10. The method of claim 9, wherein in step 1, the mass ratio of the aqueous phase to the oil phase is (3-7): 1, the mass ratio of butyl acrylate to methyl methacrylate is equal to the mass ratio; the amount of the sodium lauryl maleate is 4-8 wt% of the sum of the mass of the butyl acrylate monomer and the methyl methacrylate monomer; the amount of the initiator is 0.2-0.5 wt% of the sum of the two monomers; in step 2, the mass ratio of the water phase to the oil phase is (3-7): 1, the mass ratio of butyl acrylate to methyl methacrylate is equal to the mass ratio; the amount of the sodium lauryl maleate is 4-8 wt% of the sum of the mass of the butyl acrylate monomer and the methyl methacrylate monomer; the silver nano particles account for 2-10 wt% of the sum of the mass of the butyl acrylate monomer and the methyl methacrylate monomer.
11. The method of preparing a silver-containing nanocomposite antibacterial coating according to claim 9, wherein in the step 1 and the step 2, the mass ratio of butyl acrylate in the step 1 and the step 2 is an equal mass ratio; the mass ratio of the methyl methacrylate in the step 1 and the step 2 is equal to the mass ratio; the mass ratio of the sodium lauryl maleate in the step 1 and the step 2 is equal to the mass ratio.
12. The method of claim 9, wherein in step 3, the pre-emulsion is dropped for 0.5-1 h, the total time of emulsion polymerization is 3-4 h, the initiator is 0.2-0.5 wt% of the sum of the two monomers, and the initiator is one of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, ammonium persulfate, or potassium persulfate.
13. The method of claim 12, wherein in step 3, the initiator is potassium persulfate, and the polymerization temperature is 65-85 ℃.
14. The method of claim 13, wherein the polymerization temperature in step 3 is 70-82 ℃.
15. The method of claim 9, wherein in step 4, the substrate is a glass plate or a teflon plate, the composite emulsion is uniformly cast on the substrate, dried at room temperature of 20-25 ℃ for 24-120 h, and then dried under vacuum at 40-70 ℃ for 24-120 h to form the silver-containing nanocomposite antibacterial coating.
16. The method of claim 15, wherein the silver-containing nanocomposite antibacterial coating is formed by uniformly casting the composite emulsion on a substrate, drying the composite emulsion at room temperature of 20-25 ℃ for 48-96 hours, and vacuum drying the composite emulsion at 50-60 ℃ for 48-96 hours in step 4.
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